JP2012517362A - Regenerated butyl ionomer and regeneration method - Google Patents

Abstract

The present invention relates to a method for regenerating articles made from butyl ionomer and a method for producing regenerated butyl ionomer. The invention further relates to composites containing regenerated butyl ionomer and filler, and articles made from regenerated butyl ionomer. The present invention also relates to an uncured filled article made from a butyl ionomer having specific physical properties. Examples of fillers include silica, carbon black, talc and clay, especially onium substituted high aspect ratio nanoclays.
[Selection figure] None

Description

FIELD OF THE INVENTION The present invention relates to a method for recycling articles made from butyl ionomer and a method for producing recycled butyl ionomer. The invention further relates to composites containing reclaimed butyl ionomer and filler, and articles made from regenerated butyl ionomer. The present invention also relates to an uncured filled article made of butyl ionomer having specific physical properties.

BACKGROUND Poly (isobutylene-co (co) -isoprene) or IIR is a synthetic elastomer commonly known as butyl rubber, which has been produced by random cationic polymerization of isobutylene and small amounts (1-5 mol%) of isoprene since the 1940s. is there. IIR has excellent air impermeability, high loss modulus, oxidation stability and long-term fatigue resistance due to its molecular structure.

  Butyl rubber is understood to be a copolymer of isoolefin and one or more, preferably conjugated, multiolefins as comonomers. Commercially available butyl contains a large amount of isoolefin and a small amount, usually 2.5 mol% or less of conjugated multiolefin. Butyl rubber or butyl polymers are generally produced by a slurry process using methyl chloride as the vehicle and a Friedel-Craft catalyst as part of the polymerization initiator. This method is described in U.S. Pat. No. 2,356,128 and Ullmanns Encyclopedia of Industrial Chemistry, A23, 1993, 288-295.

  Halogenation of butyl rubber produces reactive allylic halide functionality within the elastomer. Conventional butyl rubber halogenation methods are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry (5th fully revised edition, volume A231, edited by Elvers et al.) And / or “Rubber Technology 3rd Edition” by Maurice Morton (Chapter 3 edition). Van Nostrand Reinhold Company, Copyright 1987), in particular, pages 297-300.

  The presence of allyl halide functionality allows for nucleophilic alkylation reactions. Recently, it has been shown that treatment of brominated butyl rubber (BIIR) in the solid state with nitrogen-based and / or phosphorus-based nucleophiles produces IIR-based ionomers with interesting physicochemical properties (Parent, Liskova, A .; Whitney, RA; Resendes, R., Journal of Polymer Science, Part A: Polymer Chemistry 43, 5671-5679, 2005; Parent, J. S. L .; Resendes, R., Polymer 45, 8091-8096, 2004; Parent, JS; Penciu A .; Guillen-Castellonos, SA; Riskova, A .; Whitney, RA Ma. chromolules 37, 7477-7383, 2004). The ionomer functional group is generated by the reaction of a nitrogen-based or phosphorus-based nucleophile and an allyl halide site in the halogenated butyl rubber to form an ammonium ion group or a phosphonium ion group, respectively. The physical properties of these halogenated butyl ionomers, such as raw strength, elastic modulus, interaction with fillers, etc. are superior to those of non-ionomer counterparts.

When p-methylstyrene is added to a mixed raw material for butyl polymerization (with a mixed raw material of MeCl, IB and IP together with AlCl ₃ / H ₂ O), 10 mol% or less of styrene groups are randomly added along the polymer chain. (See US Pat. No. 6,960,632; Kastas et al., Rubber Chemistry and Technology, 2001, 75, 155). Since the reactivity with isobutylene is similar, it can be seen that the molecular weight distribution is uniform. The isoprene moiety in the butyl terpolymer can be halogenated by conventional methods leading to similar type II and type III allyl halide structures as the current LANXESS halobutyl grade.

Or butyl copolymer, C ₄ ~ C ₇ isomonoolefin and p- alkylstyrene such as isobutylene, preferably contain comonomers such as p- methylstyrene. When halogenated, some of the alkyl substituents present in the styrene monomer unit contain benzylic halogens. As described in US Pat. No. 5,162,445, other functional groups can be incorporated by nucleophilic substitution of benzylic halogens with various nucleophiles. When tertiary amines and phosphines are used, butyl ionomers based on copolymers with improved physical properties are formed.

  Conventional butyl polymers containing halobutyl have the disadvantage that they must be crosslinked by curing or vulcanization in order to fully utilize their properties. However, when covalent crosslinks are formed by conventional methods (ie vulcanization), the polymer compound can no longer be reprocessed or reshaped and the remnants formed during manufacture are useless to the manufacturer and must be disposed of And can be a significant cost for manufacturers.

  Various studies have begun to produce polymers that behave like covalently crosslinked polymers at room temperature but can be easily molded at high temperatures, ie, ionic polymers. The ionic polymer can be achieved because it is crosslinked through an ionic bond with respect to a covalent bond in the same manner as an ordinary vulcanized rubber. Ionic bonds, or clusters created by ionic bonds, are disrupted by the action of shear or heat, while the covalent bonds of many conventional curing systems (vulcanization) are essentially permanent between polymer chains. It is known to be a combination of

  U.S. Pat. No. 3,646,166 describes a method for introducing carboxylic acid groups into the main chain of butyl rubber. This method can be accomplished by a multi-stage solution reaction of halobutyl dehalogenation, in which the conjugated diene is formed and then reacted with maleic anhydride, then hydrolyzed and reacted with a metal salt or amine to give an ionic heavy. Form a coalescence. This ionic polymer can be remolded with good physical properties.

  In US Pat. No. 3,898,253, a halobutyl rubber is first combined with a selected filler (silica, talc or calcium carbonate) on a warming mill and then an alkyl tertiary amine is added on a cooling mill. And then molding in a press at 175 ° C. to react the amine with the rubber to form a remoldable butyl rubber composition. Next, the obtained compound was heated on a mill to 175 ° C. and remolded to obtain a compound having some physical properties. In most cases, these physical properties were reduced by more than half.

  U.S. Pat. Nos. 4,102,876 and 4,173,695 disclose EPDM and low molecular weight formed by a multi-stage process in which sulfonation of the polymer occurs followed by quaternization with phosphonium or ammonium compounds. Methods for forming ionomers based on butyl are described. The obtained ionomer has an anionic group bound to the main chain and a cationic group as a counter ion.

  The examples outlined above have the disadvantage of long production times to form remoldable polymers while exhibiting remoldable properties (US Pat. No. 3,898,253), or the disadvantages involving multi-step synthesis. (US Pat. No. 3,646,166 and US Pat. No. 4,173,695). Furthermore, in most cases, the retention properties of the original physical properties were inferior.

  Polymer nanocomposites are a rapidly expanding field of many disciplines that represent residues to replace traditional filled polymers or polymer blends. The polymer nanocomposite is formed by mixing a nanosize inorganic filler into a polymer brazing material. Hybrid materials reinforced with raw and / or organically modified high aspect ratio plate fillers represent the most extensively studied class of nanocomposites. The strong interaction at the interface between the dispersion layer and the polymer brazing material enhances the mechanical and barrier properties for conventional composites. Maximizing high aspect ratio fillers to their highest potential requires the correct morphology and the choice of both polymer and filler is important. Internal addition of polymer to the platelet gallery, platelet delamination and exfoliation, and anisotropic alignment of the plates in the rubber brazing must be achieved. In order to achieve at least internal addition and delamination, it is advantageous to fix the chemical ink between the polymer brazing material and the filler surface.

  US patent application Ser. No. 11 / 88,172 discloses polymers, polymer compounds and composite articles comprising maleic anhydride grafted butyl polymer and montmorillonite having surprising adhesion properties. PCT / CA / 200700425 discloses a polymerization method for producing a silica-filled butyl rubber polymer in which a quaternary onium ion-substituted nanoclay is dispersed in an organic polymerization fluid before the start of polymerization.

SUMMARY OF THE INVENTION The present invention is a repeat unit derived from at least one isoolefin monomer, a repeat unit derived from at least one multiolefin monomer, and optionally copolymerizable with said isoolefin monomer or multiolefin monomer. Provided is a renewable uncured polymer composite comprising a butyl ionomer containing at least one monomer repeating unit and at least one nitrogen- or phosphorus-based nucleophile and a filler incorporated in the butyl ionomer. To do. In one embodiment, the filler contains a high aspect ratio filler, such as a nanoclay having an aspect ratio of at least 1: 3, preferably an onium substituted nanoclay. In another embodiment, the filler contains silica. The composite material may be thermoreversible, the Mooney viscosity ML (1 + 8) at 125 ° C. may be 25 Mooney units or more, and the ultimate tensile strength may be 2 MPa or more. The butyl ionomer may be partially halogenated.

  The present invention further includes a step of converting a molded article containing uncured butyl ionomer material into particles having an average size of 50 mm or more; a step of heating the particles to a temperature of 70 to 190 ° C .; There is provided a method for regenerating an uncured butyl ionomer material-containing molded article, comprising the steps of: exposing the mixture; and cooling the resulting mixture to ambient temperature. Shear mixing conditions can be supplied by a closed mixer or an extruder. The temperature is preferably in the range of 110-170 ° C.

  The present invention further includes providing a non-regenerated uncured butyl ionomer material having ultimate tensile strength at ambient temperature; heating the butyl ionomer to a temperature of 70-190 ° C .; and subjecting the butyl ionomer to shear mixing conditions for 10 seconds. There is provided a method for producing a regenerated butyl ionomer material comprising the steps of: exposing the butyl ionomer to an ambient temperature to form a regenerated butyl ionomer.

  Furthermore, the present invention provides a shaped article containing a regenerated butyl ionomer. This shaped article can exhibit an ultimate tensile strength that is less than 20% lower than the same shaped article made from a non-regenerated butyl ionomer having the same composition as the regenerated butyl ionomer. This shaped article may be made from a partially halogenated regenerated butyl ionomer.

  The present invention further provides a composite containing a regenerated butyl ionomer and a filler. This composite can exhibit an ultimate tensile strength that is less than 20% lower than a composite made from a non-regenerated butyl ionomer having the same composition as the regenerated butyl ionomer. This composite may not be cured. The composite may contain less than 50% by weight of non-regenerated butyl ionomer, preferably less than 10% by weight. Regenerated butyl ionomer may be partially halogenated. The filler may contain a high aspect ratio filler, for example a nanoclay having an aspect ratio of at least 1: 3, preferably an onium substituted nanoclay. In another embodiment, the filler may contain silica.

  The butyl ionomer composite of the present invention has superior tensile strength compared to conventional uncured butyl rubber composites and properties at least comparable to sulfur cured butyl rubber composites. When ionomers are regenerated, there is very little increase in tensile strength and molecular weight due to at least some of the selected regeneration process conditions. The composites of the present invention are particularly useful for articles such as shaped or molded articles, barriers, tank linings, shock absorbers, seals and biomedical applications.

DETAILED DESCRIPTION OF THE INVENTION Butyl ionomers are made from halogenated butyl polymers. The butyl polymer is generally derived from at least one isoolefin monomer, at least one multiolefin monomer and optionally further copolymerizable monomers.

  The butyl polymer is not limited to a specific isoolefin. However, isoolefins having 4 to 16 carbon atoms, preferably 4 to 7 carbon atoms, such as isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl -1-pentene and mixtures thereof are preferred. More preferred is isobutene (isobutylene).

The butyl rubber polymer is not limited to a specific multiolefin. Any multiolefin known to those skilled in the art that can be copolymerized with an isoolefin can be used. However, multiolefins having in the range of 4 to 14 carbon atoms such as isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperiline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2 -Neopentyl butadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, Methylcyclopentadiene, cyclohexadiene, 1-vinylcyclohexadiene and mixtures thereof, preferably conjugated dienes are used. Isoprene is more preferably used. The butyl polymers useful in the present invention include, but are not limited to, C ₁ -C ₄ alkyl substituted styrenes such as alkyl substituted aromatic comonomers including p-methyl styrene, other than the aforementioned multiolefins. Comonomers may be included.

  As the optional monomer, any monomer known to those skilled in the art that can be copolymerized with isoolefin and / or diene can be used. α-methylstyrene, p-methylstyrene, chlorostyrene, cyclopentadiene and methylcyclopentadiene are preferably used. Indene and other styrene derivatives may also be used. β-pinene can also be used as a comonomer for isoolefins. Examples of the butyl polymer may include a random copolymer of isobutylene, isoprene and p-methylstyrene.

  Preferably, the monomer mixture contains at least one isoolefin monomer in the range of about 80 to about 99% by weight and at least one multiolefin monomer in the range of about 1 to 20% by weight. More preferably, the monomer mixture contains from about 85 to about 99 weight percent isoolefin monomer and from about 1 to 15 weight percent multiolefin monomer. When the monomer mixture contains any monomer copolymerizable with isoolefin and / or diene, preferably the monomer mixture ranges from about 80 to about 99 weight percent monomer, and from about 0.5 to about 99 multiolefin monomer. In the range of 5% by weight and optional monomers in the range of about 0.5 to about 15% by weight. More preferably, the monomer mixture ranges from about 85 to about 99 weight percent isoolefin monomer, from about 0.5 to about 5 weight percent multiolefin monomer and from about 0.5 to about 10 weight percent optional monomer. Containing in the range of

  The butyl polymer can then be halogenated to produce a halobutyl polymer. Chlorination or bromination is described in methods known to those skilled in the art, for example, “Rubber Technology” 3rd edition by Maurice Morton, pages 297-300 (Kluwer Academic Publishers) and references cited therein.

  The butyl ionomer can be produced from a halogenated butyl polymer having 1.2 to 2.2 mol% of multiolefin monomer. Furthermore, the ionomer can be prepared from a high multiolefin content, for example, a butyl halide polymer exceeding 2.5 mol%, preferably exceeding 3.5 mol%, more preferably exceeding 4.0 mol%. Suitable high multiolefin butyl polymers are described in copending application CA 2,418,884, incorporated herein by reference.

  During halogenation of a butyl polymer containing a conjugated diene such as isoprene, some or all of the multiolefin content of the butyl polymer is converted to an allyl halide. The total allyl halide content in the halobutyl polymer cannot exceed the starting multiolefin content of the parent butyl polymer. At the allyl halide site, it can react with the halobutyl polymer to bind the nucleophile. For halobutyl polymers that do not contain an allyl halide, such as halobutyl polymers derived from isobutylene and styrenic monomers, the benzylic halide formed by halogenation of the styrenic monomer reacts. Thus, ionomers can be formed rather than allyl halides. Thus, the same reasoning applies to benzyl halides as allyl halides, and the total amount of ionomer moieties cannot exceed the availability of benzyl halides.

In one embodiment of the present invention, the allyl halide moiety or benzyl halide moiety of the halobutyl polymer has the formula:

And at least one nucleophile containing nitrogen or phosphorus. In the formula, A is nitrogen or phosphorus, and R ₁ , R ₂ , and R ₃ are linear or branched C _{1 to} C ₁₈ alkyl substituents, monocyclic or C _{4 to} C ₈ condensed rings Aryl substituents, and / or selected from the group consisting of heteroatoms selected from, for example, B, N, O, Si, P and S.

  In general, suitable nucleophiles have at least one neutral nitrogen or phosphorus center with a lone pair of electrons that can be applied both electronically and sterically to participate in nucleophilic substitution reactions. Suitable nucleophiles include trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine 2-dimethylaminoethanol, 1- Dimethylamino-2-propanol, 2- (isopropylamino) ethanol, 3-dimethylamino-1-propanol, N-methyldiethanolamine, 2- (diethylamino) ethanol, 2-dimethylamino-2-methyl-1-propanol, 2 -[2- (dimethylamino) ethoxy] ethanol, 4- (dimethylamino) -1-butanol, N-ethyldiethanolamine, triethanolamine, 3-diethylamino-1-propanol, 3 -(Diethylamino) -1,2-propanediol, 2-{[2-diethylamino] ethyl} methylamino} ethanol, 4-diethylamino-2-butyn-1-ol, 2- (diisopropylamino) ethanol, N-butyldiethanolamine N-tert-butyldiethanolamine, 2- (methylphenylamino) ethanol, 3- (dimethylamino) benzyl alcohol, 2- [4- (dimethylamino) phenyl] ethanol, 2- (N-ethylamino) ethanol, N -Benzyl-N-methylethanolamine, N-phenyldiethanolamine, 2- (dibutylamino) ethanol, 2- (N-ethyl-Nm-toluidino) ethanol, 2,2 '-(4-methylphenylamino) diethanol Tris [2- [2- (methoxyethoxy) ester Til] amine, 3- (dibenzylamino) -1-propanol and mixtures thereof.

  The amount of nucleophile reacted with the butyl polymer is 0.05 to 5 molar equivalents, more preferably 0.5 to 5 based on the total molar amount of allyl halide or benzyl halide present in the halobutyl polymer. It may be in the range of 4 molar equivalents, still more preferably 1-3 molar equivalents.

  The halobutyl polymer and nucleophile can react for about 0.5 to 90 minutes. When the reaction takes place in an extruder, the reaction time is preferably 10 to 120 seconds, more preferably 20 to 60 seconds. When the reaction takes place in a closed mixer, the reaction time is preferably 1 to 15 minutes, more preferably 1 to 4 minutes. In other cases, the reaction time is quite long, e.g. greater than 15 minutes and less than 90 minutes, preferably 20-60 minutes. The temperature is preferably 80 to 200 ° C.

  As described above, the nucleophile reacts with the allyl halide or benzyl halide functionality of the halobutyl polymer, and the unit of the ionomer moiety is present in the presence of the allyl halide or benzyl halide functionality on the halobutyl polymer. Arise. The total content of ionomer moieties in the butyl ionomer cannot exceed the starting amount of allyl halide or benzyl halide in the halobutyl polymer, but residual allyl halide and / or residual multiolefin may be present. In embodiments of the invention where almost all allylic halide or benzyl halide moieties are reacted with nucleophiles, butyl ionomers are formed. In embodiments where less than the total allyl halide or benzyl halide moiety reacts with the nucleophile, a partially halogenated butyl ionomer is formed.

  The resulting ionomer preferably has an ionomer moiety of 0.5 mol% or more, preferably 0.75 mol% or more, more preferably 1.0 mol% or more, and still more preferably 1.5 mol% or more. The residual allyl halide may be present in an amount from 0.1 mol% up to an amount not exceeding the original allyl halide content in the halobutyl polymer used in the production of the butyl ionomer. Residual multiolefin may be present in an amount from 0.1 mol% up to an amount not exceeding the original multiolefin content in the butyl polymer used to make the halobutyl polymer. Usually, the content of residual multiolefin in the ionomer is 0.4 mol% or more, preferably 0.6 mol% or more, more preferably 1.0 mol% or more, still more preferably 2.0 mol% or more, Still more preferably, it is 3.0 mol% or more, and still more preferably 4.0 mol% or more.

  The partially halogenated butyl ionomer may then be cured using a conventional curing system such as sulfur or zinc oxide. If residual multiolefin is also present, a peroxide cure system may be used. However, as shown herein, the ionomer network structure can advantageously provide uncured articles having useful physical properties such as ultimate tensile strength, ultimate elongation, and / or Mooney viscosity. Such uncured (or slightly cured) articles have the additional advantage of being reproducible at high temperatures under shear mixing conditions. The regeneration methods and regeneration ionomers described herein surprisingly show little degradation of physical properties even in multiple recycling iterations. Thus, this regeneration method and regeneration ionomer are very advantageous from an environmental and economic point of view.

  In order to regenerate the uncured butyl ionomer described herein, the uncured butyl ionomer is obtained from 80-200 ° C, more preferably 100-190 ° C, even more preferably 110-180 ° C, still more preferably 120-120 ° C. Supplied to a shear mixing device capable of raising the temperature to 170 ° C. This high temperature can be supplied by an external heat source and / or can be generated by shear mixing of highly viscous butyl ionomers. This temperature should be high enough to reduce the ionomer's viscosity to a point where it can be mixed without applying excessive power, but if the temperature is too high, the molecular weight of the ionomer will be reduced and the Mooney viscosity will be reduced. Occurs. The above temperature range is particularly well suited for butyl ionomers for regeneration having an initial Mooney viscosity (ML 1 + 8 @ 125 ° C.) of 25 to 35 Mooney units.

  The butyl ionomer is exposed to shear mixing conditions for 10 seconds or more, preferably 15 minutes or less. This amount of time depends on the degree of shear imparted by the selected mixing method. When an extruder is used, high shear can be obtained in a short time, usually 10 to 60 seconds. Sealed mixers such as Banbury or Haake closed mixers usually require long mixing times of more than 1 minute and not more than 15 minutes, preferably 1 to 10 minutes, more preferably about 1 to 5 minutes. If the mixing time is too long, the molecular weight of the ionomer is reduced, which may cause a decrease in Mooney viscosity. The mixing time is particularly well suited for butyl ionomers for regeneration having an initial Mooney viscosity ML (1 + 8) @ 125 ° C. of 25 to 35 Mooney units.

  When the butyl ionomer is supplied to the regeneration process as a shaped or molded article, it is generally necessary to convert such an article into particles so that it can be supplied to a shear mixing device. Methods for converting the article into particles include a chipping, crushing, cutting or hammering process, optionally assisted by cryogenic freezing of the article with liquid nitrogen, for example. The average particle size is 50 mm or less, preferably 25 mm or less, more preferably 10 mm or less, and still more preferably 1 mm or less. Smaller particle sizes generally require less time for the regeneration method, but large-capacity regeneration energy inputs may be quite expensive. The average particle size is determined based on the Sauter average diameter of the particles. The particles do not necessarily have to be circular, but may be elongated or irregularly shaped.

  When this regeneration method is used for the production of regenerated butyl ionomer from non-regenerated (or unused) butyl ionomer, it is desirable that the deterioration of physical properties is minimized. The ultimate tensile strength of the regenerated butyl ionomer is preferably 60% or more, more preferably 80% or more, and still more preferably 90% or more with respect to the ultimate tensile strength of the non-regenerated butyl ionomer. The ultimate tensile strength of the non-regenerated butyl iono is preferably 2 MPa or more, more preferably 3 MPa or more, still more preferably 5 MPa or more, still more preferably 8 MPa or more, and still more preferably 10 MPa or more. The ultimate tensile strength of the regenerated butyl iono is preferably 1 MPa or more, more preferably 2 MPa or more, still more preferably 3 MPa or more, still more preferably 4 MPa or more, still more preferably 6 MPa or more, still more preferably 8 MPa or more, still more. Preferably it is 10 MPa or more. When the butyl ionomer is filled, a high ultimate tensile strength can be obtained. This strength depends at least in part on the choice of filler and the amount of filler. Non-regenerated butyl ionomers are uncured, and regenerated butyl ionomers are preferably uncured to allow further regeneration iterations, but in certain instances these butyl ionomers may be cured. If the non-regenerated butyl ionomer is partially halogenated, the regenerated ionomer may be cured, or as described above, the content of the ionomer moiety may be further increased by reaction with a nitrogen or phosphorus nucleophile. Also good. This occurs during high temperature and shear mixing conditions during the regeneration process.

  The conditions for the regeneration method are usually selected so as to prevent a decrease in molecular weight. The Mooney viscosity ML (1 + 8) @ 125 ° C. of the regenerated butyl ionomer is preferably 50% or more, more preferably 70% or more, and still more preferably 80% or more of the non-regenerated butyl ionomer. The ultimate elongation of the regenerated butyl ionomer is preferably 500% or more, more preferably 600% or more, and still more preferably 700% or more.

  Regenerated butyl ionomers produced using the above method can be used to form shaped articles. The shaped article may be more recyclable (ie thermoreversible). The shaped article may be filled or unfilled. The shaped article may contain a high aspect ratio filler. A shaped article made from recycled butyl ionomer may be subsequently cured if residual halogenation is present in the recycled butyl ionomer.

  Regenerated butyl ionomer can be used to form filled composites. This composite exhibits an ultimate tensile strength that is less than 20% lower than a composite made from a non-regenerated butyl ionomer having the same composition as the regenerated butyl ionomer. The composite may contain less than 50% by weight of non-regenerated ionomer, preferably less than 10% by weight. The composite may contain a filler having a high aspect ratio, for example an aspect ratio of at least 1: 3. The filler may contain clay, such as onium substituted nanoclay. The particle size of the nanoclay may be 1-50 μm, preferably 1-25 μm.

In general, fillers suitable for use in the present invention are composed of inorganic or non-inorganic particles. Suitable fillers include silica, silicates, clays (such as bentonite), gypsum, alumina, titanium dioxide, talc, and the like, and mixtures thereof. Another example of a suitable filler is as follows.

- For example the silicate solution precipitation, or in a highly dispersed silicas, prepared by flame hydrolysis of silicon halides, with specific surface areas (BET specific surface area) is 5~1000m ² / g, preferably in the range from 20 to 400 m ² / g, mainly The particle size is in the range of 10 to 400 nm. This silica may optionally be present as a mixed oxide with oxides of other metals such as Al, Mg, Ca, Ba, Zn, Zr and Ti.

Synthetic silicates such as aluminum silicate and alkaline earth metal silicates.
Magnesium silicate or calcium silicate having a BET specific surface area of 20 to 400 m ² / g and a main particle size of 10 to 400 nm.
• Natural silicates such as kaolin and other naturally occurring silicas.
• Natural clays such as montmorillonite and other natural clays.

• Organophilically modified montmorillonite clay (eg Cloisite® obtained from Southern Clay Products) and other organophilically modified natural clays.
・ Glass fiber and glass fiber product (mat, extrudate) or micro glass sphere.

Metal oxides such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide.
Metal carbonates such as magnesium carbonate, calcium carbonate and zinc carbonate.
Metal hydroxides such as aluminum hydroxide and magnesium hydroxide or combinations thereof.

  Since these inorganic particles have a hydroxyl group on the surface and make the particles hydrophilic and oleophobic, it is difficult to improve the interaction between the filler particles and the butyl elastomer. For many purposes, the preferred mineral is silica, particularly silica made by carbon dioxide precipitation of sodium silicate.

The average aggregate particle size of the dry amorphous silica particles suitable for use in the present invention is in the range of 1-100 [mu], preferably 10-50 [mu], more preferably 10-25 [mu]. A particle size of less than 10% by volume of the aggregate particles is preferably less than 5μ or greater than 50μ. Suitable amorphous dry silicas more usually have a BET surface area measured according to DIN (German Industrial Standard) 66131 in the range of 50-450 m ² / g and a DBP absorption measured according to DIN 53601 of 150-400 g / It is in the range of 100 g silica and the loss on drying measured according to DIN ISO 787/11 is in the range of 0 to 10% by weight. Suitable silica fillers are available from PPG Industries Inc. Under the trade names HiSil 210, HiSil 233 and HiSil 243. Also suitable are Vulkasil ™ S and Vulkasil ™ N commercially available from Bayer AG.

The inorganic filler can be used alone or in combination with the following known non-inorganic fillers.
·Carbon black. Suitable carbon blacks are preferably produced by the lamp black method, furnace black method or gas black method and have a BET specific surface area of 20 to ²⁰⁰ m ² / g, for example SAF, ISAF, HAF, FEF or GPF carbon black.
Rubber gels, preferably rubber gels based on polybutadiene, butadiene / styrene copolymers, butadiene / acrylonitrile copolymers and polychloroprene.

High aspect ratio fillers useful in the present invention include silica, clay, talc, mica and the like with an aspect ratio of at least 1: 3. The filler may contain a non-circular or non-isomeric material having a plate-like or needle-like structure. Aspect ratio is defined as the ratio of the average diameter of a circle in the same area as the plane of the plate to the average thickness of the plate. The aspect ratio of acicular and fibrous fillers is the length: diameter ratio. The aspect ratio of the high aspect ratio filler is preferably at least 1: 5, more preferably at least 1: 7, and even more preferably 1: 7 to 1: 200. The average particle size of the filler according to the present invention is in the range of 0.001 to 100 μ, preferably 0.005 to 50 μ, more preferably 0.01 to 10 μ. The BET surface area of suitable fillers is in the range from 5 to 200 m ² / g, measured according to DIN (German Industrial Standard) 66131. Some preferred fillers and their properties are shown in Table 1 in comparison with conventional fillers having an aspect ratio of less than 1: 3.

Preferred embodiments of high aspect ratio fillers include nanoclays, preferably organically modified nanoclays. However, the present invention is not limited to specific nanoclays, and natural powdered smectite clays such as sodium montmorillonite or calcium montmorillonite, or synthetic clays such as hydrotalcite and laponite are preferred as starting materials. Organic modified montmorillonite nanoclay is particularly preferred. These clays, as is known in the art, are generally modified by substitution of transition metals for onium ions to impart to the clay surface active functionality that promotes dispersion of the clay within the hydrophobic polymer environment. Is preferable. Preferred onium ions are phosphorus-based (for example, phosphonium ion) and nitrogen-based (for example, ammonium ion), and have a functional group having 2 to 20 carbon atoms (for example, NR ₄ ⁺ -MMT).

The clay is supplied with a nanometer scale particle size, preferably less than 25 μm volume, more preferably 1-50 μm, even more preferably 1-30 μm, still more preferably 2-20 μm.
In addition to silica, preferred nanoclays may also contain some alumina fraction. The nanoclay may contain 0.1 to 10 wt% alumina, preferably 0.5 to 5 wt%, more preferably 1 to 3 wt%.

  Examples of commercially preferred organic modified nanoclays suitable for use as the high aspect ratio fillers of the present invention are Cloisite® 10A, 20A, 6A, 15A, 30B or 25A. The high aspect ratio filler is added to the nanocomposite from 3 to 80 phr, more preferably from 5 to 30 phr, and even more preferably from 5 to 15 phr. Nanocomposites are formed by adding additives to preformed ionomers using conventional compounding techniques.

  The composite may be formed by regeneration of filled uncured ionomer, or by regeneration of unfilled uncured ionomer and then introduction of a filler. Two or more fillers may be supplied to the composite material. The components of the composite can be mixed using, for example, a closed mixer such as a Banbury mixer, a small closed mixer such as a Haake or Brabender mixer, or a two roll mill mixer. The extruder can be mixed well in a short time. It is possible to carry out the mixing in two or more stages, in which case the mixing can be carried out in different apparatuses, for example one stage with a closed mixer and one stage with an extruder. See Encyclopedia of Polymer Science and Engineering, Vol. 4, page 66 et seq. (Formulation) for further compounding techniques.

  The composite material can be formed into a model by molding, for example. The shaped article may be cured as described above. The composite may be supplied as a masterbatch for subsequent downstream processing. The composite may be mixed with a non-regenerated ionomer or a conventional halogenated or non-halogenated butyl polymer and then formed into a shaped article.

  The present invention will be described with respect to the formation of thermoreversible filled butyl-based compounds having excellent properties and a method for regenerating butyl ionomer. The following examples illustrate specific embodiments of the present invention.

Laboratory instrument:
Hardness and stress-strain properties were measured using an A-2 durometer in accordance with ASTM D-2240 requirements. Stress strain data was obtained at 23 ° C. according to the requirements of ASTM D-412 Method A. A die C dumbbell cut from a 2 mm thick tensile sheet was used. A thermoset was formed at a pressure of 15,000 psi at 166 ° C. for a total of 30 minutes, and an ionomer was molded at a pressure of 15,000 psi at 160 ° C. for a total of 12 minutes. ¹ H NMR spectra were recorded in CDCl ₃ with chemical shifts with reference to tetramethylsilane using a Bruker DRX500 spectrometer (500.13 MHz).

material:
Unless otherwise noted, all reagents were received from Sigma-Aldrich (Oakville, Ontario). Used from BIIR (LANXESS BB2030 ^™ , LANXESS Inc.), Sunpar 2280 ^™ (RE Carroll Inc.), Pentalyn A ^™ (Hercules), Vulkacit DM / C ^™ (LANXESS Inc.). Carbon black N660 ^™ (Sid Richardson Carbon and Gas Companies), Closite 15A ^™ (Sourthern Cray Products), and Hi-Sil 233 ^™ (PPG Industries, Inc.) were used from their respective suppliers.

Example 1: Preparation of IIR-PPh ₃ Br ionomer 356 g of BIIR (LANXCESS BB2030C, LANXCESS Inc.) and 16.7 g of triphenylphosphine (TPP) (1.2 molar equivalents relative to the brominated allyl content) 6 "x 12 “Premixed on the mill for 3 minutes at room temperature. The mixture was then heated on the same mill at 100 ° C. for 1 hour. ¹ HNMR analysis of the final product confirmed complete conversion of all BB2030 allyl bromide to the corresponding ionomer species.

Examples 2-7
The following examples show the effect of ionomers on the physical properties of vulcanized carbon black filled systems compared to the physical properties of non-ionomer systems of the same formulation. Examples 2, 4 and 6 were prepared by mixing Example 1 and carbon black N660 in a Brabender mixer at 60 ° C. and a rotor speed of 60 rpm for 15 minutes. Examples 3, 5, and 7 were prepared in the same manner except that BB2030 was used instead of Example 1. The resulting blend was molded and the tensile properties were measured as described above. The results are shown in Table 2.

  As shown in Table 2, the phosphonium ionomer (Examples 2, 4, and 6) has increased reinforcement and markedly improved tensile strength as compared to the non-ionomer system (Examples 3, 5, and 7).

Examples 8-13
The following examples show the effect of an ionomer network on the properties of an unvulcanized silica-filled system as compared to non-ionomer based properties of the same formulation. The manufacture of Examples 8, 10, and 12 was performed as described in Example 2, and the manufacture of Examples 9, 11, and 13 was performed as described in Example 3. The resulting blend was molded and the tensile strength was measured as described above. The results are shown in Table 3.

  As shown in Table 3, phosphonium ionomers (Examples 8, 10, and 12) have increased reinforcement and significantly improved tensile strength compared to non-ionomer systems (Examples 9, 11, and 13). .

Examples 14-19
The following examples show the effect of an ionomer network on the physical properties of an unvulcanized clay filled system as compared to the physical properties of a non-ionomer system of the same formulation. Examples 14, 16, and 18 were prepared as described in Example 2, and Examples 15, 13, and 17 were manufactured as described in Example 3. The resulting blend was molded and the tensile properties were measured as described above. The results are shown in Table 4.

  As shown in Table 4, the phosphonium ionomer (Examples 14, 16, and 18) increased in reinforce and significantly improved tensile strength compared to the non-ionomer system (Examples 15, 17, and 19).

Example 20
The following examples show the effect of a phosphonium bromide ionomer network on the unvulcanized physical properties compared to conventional sulfur cured thermosetting resins. In Example 20, BB2030 and carbon black N660 were mixed at 30 ° C. and a rotor speed of 77 rpm for 1 minute in a Banbury mixer, and then the oil and the accelerator were added, mixed for another 4 minutes, and then taken out. Next, curing agents (sulfur, stearic acid, and zinc oxide) were added on a two roll 10 "x 20" mill at room temperature. The resulting formulation was cured and the tensile properties were measured as described above. The results are shown in Table 5.

  As shown in Table 5, the unvulcanized phosphonium ionomer system (Examples 4, 12, 16) has comparable properties compared to the standard tire liner formulation (Example 20). In the case of silica-clay filled ionomer systems, significant improvements in ultimate tension and ultimate elongation were observed.

Examples 21-25
The following example demonstrates the recyclability of unvulcanized silica filled phosphonium bromide ionomer. Example 12 was remixed in a Brabender mixer at a temperature of 160-170 ° C. for 15 minutes and remolded under the same conditions to produce Example 21 (first recycled product). Example 21 was then remixed and reshaped to produce Example 22 (second recycled product). Example 22 was then remixed and reshaped to produce Example 23 (third recycled product). Example 23 was then remixed and reshaped to produce Example 24 (fourth recycled product). Example 24 was then remixed and reshaped to produce Example 25 (fifth recycled product). Table 6 shows the tensile properties.

As shown in Table 6, the tensile strength was kept very good after each regeneration.

Examples 26-30
The following example demonstrates the reproducibility of unvulcanized clay filled phosphonium bromide ionomer. Example 16 was remixed in a Brabender mixer at a temperature of 160-170 ° C. for 15 minutes and remolded under the same conditions to produce Example 26 (first recycled product). Example 26 was then remixed and reshaped to produce Example 27 (second recycled product). Example 27 was then remixed and reshaped to produce Example 28 (third recycled product). Example 28 was then remixed and reshaped to produce Example 29 (fourth recycled product). Example 29 was then remixed and reshaped to produce Example 30 (fifth recycled product). Table 7 shows the tensile properties.

As shown in Table 7, the tensile strength was maintained very well after each regeneration.

Examples 31-35
The butyl terpolymer was prepared by the method described in Kaszas US Pat. No. 6,960,632; Kaszas et al., Rubber Chemistry and Technology, 2001, 75, 155. The final product has 10 mol% pMeSt and 2 mol% IP. This was brominated using standard methods (Br _{2 in} hexane) to give a brominated butyl terpolymer having 0.8 moles of allyl bromide and a Mooney viscosity of 30 MU. The amount of allyl bromide and the remaining 1,4-isoprene is similar to that of commercially available BB2030. The resulting brominated terpolymer was then reacted with dimethylaminoethanol (3.2 molar equivalents) at 160 ° C. in a twin screw extruder. ¹ H NMR analysis of the final product confirmed that all of the allyl bromide was completely converted to the corresponding ionomer species. High Sil 233 (50 phr) was then placed in a Brabender mixer and mixed for 15 minutes at 60 ° C. and rotor speed 60 rpm. Example 31 was remixed in this Brabender at a temperature of 160-170 ° C. for 15 minutes and remolded under the same conditions to produce Example 32 (first recycled product). Example 32 was then remixed and reshaped to produce Example 33 (second recycled product). Example 33 was then remixed and reshaped to produce Example 34 (third recycled product). Example 34 was then remixed and reshaped to produce Example 35 (fourth recycled product). Table 8 shows the tensile properties.

As shown in Table 8, the tensile strength was maintained very well after each regeneration.

Examples 36-41
The following example shows the effect of an ionomer network on the physical properties of an unvulcanized inorganic filler system compared to the physical properties of a non-ionomer system having the same formulation. Examples 36, 38, and 40 were manufactured in the same manner as in Example 2, and Examples 37, 39, and 41 were manufactured in the same manner as in Example 3. The resulting blend was molded and the tensile properties were measured as described above. The results are shown in Table 9.

Examples 42-47
The following examples show the effect of increasing the ionomer content on the polymer backbone on the physical properties of the unvulcanized silica filled system. LANXESS BB2030: 356 g is blended with 3.5 g PPh ₃ (Example 42), 7.0 g (Example 43) and 10.5 g (Example 44) to give allyl bromide functionality -25%, 50% and 75 For 3 minutes on a room temperature mill. The mixture was then passed through a small twin screw extruder (160 ° C., 20 rpm) and purified on a room temperature mill. These ionomers were characterized by NMR analysis to determine the amount of ionomer groups along the polymer backbone. Examples 42-44 and Hi Sil 233 were mixed in a Brabender mixer at 60 ° C. and rotor speed 60 rpm for 15 minutes to produce Examples 45-47. The resulting blend was molded and the tensile properties were measured as described above. The results are shown in Table 10.

Example _{48: IIR-N (CH 2} CH 2 OH) 3 prepared in Br ionomer
LANXESS BB2030 was fed to a small twin screw extruder (160 ° C., 20 rpm) along with N, N-dimethylamino alcohol (3.22 molar equivalents relative to the allyl bromide content). The extrudate was purified on the mill and analyzed by NMR to confirm that all of the BB2030 allyl bromide was completely converted to the corresponding ionomer species.

Examples 49-51
The following examples show the effect of an ammonium-based ionomer network on the compound properties of filled uncured materials containing various inorganic fillers. Examples 49, 50, and 51 were prepared by mixing Example 48 with carbon black N660, Hi Sil 233, and Cloisite 15A in a Brabender mixer at 60 ° C. and a rotor speed of 60 rpm for 15 minutes, respectively. The resulting blend was molded and the tensile properties are shown in Table 11.

Example 52: Preparation of brominated isobutylene p-methylstyrene copolymer (BIMS) based phosphonium ionomer
Exxpro 3435: 150 g was compounded with 10 g PPh ₃ on a room temperature mill for 3 minutes. The mixture was then passed through a small twin screw extruder (160 ° C., 20 rpm) and purified on a room temperature mill. NMR analysis of the resulting material confirmed complete conversion of the benzyl bromide group of Exxpro 3435 to the corresponding ionomer species.

Example 53: Preparation of brominated isobutylene p-methylstyrene copolymer (BIMS) based ammonium ionomer
Exxpro 3435 was fed to a small twin screw extruder (160 ° C., 20 rpm) along with N, N-dimethylamino alcohol (3.22 molar equivalents relative to the allyl bromide content). The extrudate was purified on the mill and analyzed by NMR, confirming that all of the benzyl bromide groups of BB2030 were completely converted to the corresponding ionomer species.

Examples 54-57
The following examples show the effect of an ionomer network on the compound properties of filled uncured materials containing various inorganic fillers. All the mixtures were prepared in a Brabender mixer by mixing for 15 minutes at 60 ° C. and a rotor speed of 60 rpm. Examples 54 and 55 were prepared by mixing Exxpro 3435 and Example 52 with carbon black N660, respectively. Examples 56 and 57 were prepared by mixing Exxpro 3435 and Example 52 with Hi Sil 233 and carbon black N660, respectively. The resulting blend was molded and the tensile properties are shown in Table 12.

  Although the present invention has been described in detail above, these details are for illustrative purposes only, and those skilled in the art will understand the spirit and scope of the invention, except as may be limited by the claims. It is understood that various changes can be made without departing from the above.

US Pat. No. 2,356,128 US Pat. No. 6,960,632 US Pat. No. 5,162,445 U.S. Pat. No. 3,646,166 U.S. Pat. No. 3,898,253 U.S. Pat. No. 4,102,876 US Pat. No. 4,173,695 U.S. Pat. No. 3,898,253 US patent application Ser. No. 11 / 88,172 PCT / CA / 200700425

Ullmanns Encyclopedia of Industrial Chemistry, A23, 1993, 288-295. Ullmann's Encyclopedia of Industrial Chemistry (5th fully revised edition, volume A231, edited by Elvers, etc.) “Rubber Technology” (3rd edition) by Maurice Morton, Chapter 10 (Van Nostrand Reinhold Company, Copyright 1987), especially 297-300. Parent, J. et al. S. Liskova, A .; Whitney, R .; A. Resendes, R .; , Journal of Polymer Science, Part A Polymer Chemistry 43, 5671-5679, 2005 Parent, J. et al. S. Liskova, A .; Resendes, R .; , Polymer 45, 8091-8096, 2004 Parent, J. et al. S. Penciu A .; Guillen-Castellonos, S .; A. Liskova, A .; Whitney, R .; A. , Macromolecules 37, 7477-7383, 2004. Kaszas et al., Rubber Chemistry and Technology, 2001, 75, 155. Encyclopedia of Polymer Science and Engineering, Vol. 4, page 66 and below (formulation)

Claims (59)

a. Converting the molded article containing the uncured butyl ionomer material into particles having an average size of 50 mm or more;
b. Heating the particles to a temperature of 80-200 ° C;
c. Exposing the particles to shear mixing conditions for 10 seconds or more; and d. Cooling the resulting mixture to ambient temperature;
A method for regenerating a molded product containing an uncured butyl ionomer material.   The method of claim 1, wherein the ionomer is filled with a filler.   The method according to claim 1 or 2, wherein the shear mixing conditions are supplied using a closed mixer or an extruder.   The method according to any one of claims 1 to 3, wherein the temperature is 110 to 180 ° C.   The method of any one of claims 1-4, wherein the particles are exposed to shear mixing conditions for 15 minutes or less.   The method according to any one of claims 1 to 5, wherein the ionomer is partially halogenated. a. Providing a non-regenerated uncured butyl ionomer material having ultimate tensile strength at ambient temperature;
b. Heating the butyl ionomer to a temperature of 80-200 ° C;
c. Exposing the butyl ionomer to shear mixing conditions for 10 seconds or more; and d. Cooling the butyl ionomer to ambient temperature to form a regenerated butyl ionomer;
A method for producing a recycled butyl ionomer material comprising:   The method according to claim 7, wherein the ultimate tensile strength of the regenerated butyl ionomer is 60% or more of the ultimate tensile strength of the non-regenerated butyl ionomer.   The method according to claim 7, wherein the ultimate tensile strength of the non-regenerated butyl ionomer is 10 MPa or more.   The method according to claim 7 or 9, wherein the ultimate tensile strength of the regenerated butyl ionomer is 6 MPa or more.   11. A method according to any one of claims 7 to 10, wherein the non-regenerated butyl ionomer is filled with a filler.   12. A method according to any one of claims 7 to 11 wherein the regenerated butyl ionomer is not cured.   The method according to any one of claims 7 to 12, wherein the non-regenerated butyl ionomer is partially halogenated.   14. The method of claim 13, further comprising adding a nitrogen-based or phosphorus-based nucleophile while exposing the butyl ionomer to shear mixing conditions.     The method according to claim 14, wherein the content of the ionomer moiety in the regenerated butyl ionomer is greater than the content of the ionomer moiety in the non-regenerated butyl ionomer.   The method according to any one of claims 7 to 15, further comprising forming the regenerated butyl ionomer to form an article.   The method according to any one of claims 7 to 16, wherein the shear mixing conditions are supplied in a closed mixer or an extruder.   The method according to any one of claims 7 to 17, wherein the non-regenerated butyl ionomer has a Mooney viscosity ML (1 + 8) at 125 ° C of 25 Mooney units or more.   The method according to any one of claims 7 to 18, wherein the regenerated butyl ionomer has a Mooney viscosity ML (1 + 8) at 125 ° C of 70% or more of the non-regenerated butyl ionomer's Mooney viscosity.   A thermoreversible article made from uncured filled butyl ionomer having a Mooney viscosity ML (1 + 8) at 125 ° C. of 25 Mooney units or more and an ultimate tensile strength of 2 MPa or more.   A shaped product containing recycled butyl ionomer.   The shaped article according to claim 21, wherein the shaped article exhibits an ultimate tensile strength that is less than 20% lower than the same shaped article made from a non-regenerated butyl ionomer having the same composition as the regenerated butyl ionomer.   The shaped article according to claim 21, wherein the ultimate tensile strength of the shaped article is 6 MPa or more.   The shaped article according to claim 22, wherein the ultimate tensile strength of the shaped article is 8 MPa or more.   The shaped article according to any one of claims 21 to 24, wherein the butyl ionomer is filled with a filler.   The shaped article according to any one of claims 21 to 25, wherein the shaped article is not cured.   The shaped article according to claim 25, wherein the shaped article is not cured.   The shaped article according to any one of claims 21 to 25, wherein the regenerated butyl ionomer is partially halogenated.   The shaped article according to claim 28, wherein the shaped article is cured.   The molded article according to any one of claims 21 to 29, wherein the ultimate elongation of the regenerated butyl ionomer is 600% or more.   A composite material containing a regenerated butyl ionomer and a filler.   32. The composite of claim 31, wherein the composite exhibits an ultimate tensile strength that is less than 20% lower than a composite made from a non-regenerated butyl ionomer having the same composition as the regenerated butyl ionomer.   The composite material according to claim 31 or 32, wherein the ultimate tensile strength of the composite material is 8 MPa or more. The composite material according to any one of claims 31 to 33, wherein the composite material is not cured. 34. The composite material according to any one of claims 31 to 33, wherein the composite material is cured.   The composite material according to any one of claims 31 to 35, wherein the composite material contains less than 50% by weight of non-regenerated butyl ionomer.   37. The composite of claim 36, wherein the composite contains less than 10% by weight of non-regenerated butyl ionomer.   The composite material according to any one of claims 31 to 35, wherein the regenerated butyl ionomer is partially halogenated.   39. The composite of any one of claims 31 to 38, wherein the butyl ionomer comprises repeat units derived from at least one isoolefin monomer and repeat units derived from at least one multiolefin monomer.   The isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and mixtures thereof. Item 40. The composite material according to Item 39.   The multiolefin monomer is isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperiline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl- 1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1- 41. A composite according to claim 39 or 40 selected from the group consisting of vinylcyclohexadiene and mixtures thereof.   The composite material according to any one of claims 39 to 41, wherein the butyl ionomer further comprises a repeating unit of at least one monomer copolymerizable with the isoolefin monomer or multiolefin monomer.   The at least one monomer copolymerizable with the isoolefin monomer or multiolefin monomer is selected from the group consisting of α-methylstyrene, p-methylstyrene, chlorostyrene, cyclopentadiene, methylcyclopentadiene, and mixtures thereof. 42. The composite material according to 42.   43. The composite according to claim 39 or 42, wherein the multiolefin monomer is selected from the group consisting of [alpha] -methylstyrene, p-methylstyrene, chlorostyrene, cyclopentadiene, methylcyclopentadiene, and mixtures thereof.   The butyl ionomer polymerizes the monomers to form a butyl polymer, halogenates the butyl polymer to form a halobutyl polymer, and then converts the halobutyl polymer to at least one nitrogen-based or phosphorus-based polymer. The composite material according to any one of claims 39 to 44, which is formed by reacting with a nucleating agent.   46. The composite material according to any one of claims 39 to 45, wherein the filler is a high aspect ratio filler.   47. The composite of claim 46, wherein the high aspect ratio filler has an aspect ratio of at least 1: 3.   48. The composite of claim 47, wherein the high aspect ratio filler has an aspect ratio of at least 1: 5.   49. The composite of claim 48, wherein the aspect ratio of the high aspect ratio filler is at least 1: 7. 50. The composite of claim 49, wherein the high aspect ratio filler has an aspect ratio of at least 1: 7 to 1: 200.   51. A composite according to any one of claims 46 to 50, wherein the high aspect ratio filler is selected from the group consisting of silica, clay, talc and mica. 52. The composite of claim 51, wherein the high aspect ratio filler is nanoclay.   53. The composite according to claim 52, wherein the nanoclay is an organically modified nanoclay.   54. The composite material according to claim 52 or 53, wherein the nanoclay has a particle size of less than 25 [mu] m.   54. The composite material according to claim 52 or 53, wherein the nanoclay has a particle size of 1 to 50 [mu] m.   A repeating unit derived from at least one isoolefin monomer, a repeating unit derived from at least one multiolefin monomer, and optionally at least one monomer copolymerizable with said isoolefin monomer or multiolefin monomer; And a renewable uncured polymer composite comprising a butyl ionomer containing at least one nitrogen-based or phosphorus-based nucleophile and a filler mixed in the butyl ionomer.   57. The composite of claim 56, wherein the filler comprises a high aspect ratio filler having an aspect ratio of at least 1: 3.   58. The composite of claim 57, wherein the filler comprises onium substituted nanoclay.   57. The composite material according to claim 56, wherein the filler contains silica.